Photochemical (Hetero-)Arylation of Aryl Sulfonium Salts

[Image: see text] The construction of (hetero)biaryls, which are ubiquitous scaffolds among medical substances, functional materials, and agrochemicals, constitutes a key application of cross-coupling methods. However, these usually require multiple synthetic steps. Herein, we report a simple photoinduced and catalyst-free C–H/C–H (hetero)arylation cross-coupling through aryl thianthrenium salts, which are formed site-selectively by direct C–H functionalization. The key to this approach is the UV-light, which can disrupt the C–S bond to form thianthrene radical cations and aryl radicals.